三聚氰胺氰脲酸阻燃尼龙66热降解行为及动力学
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摘要
在对三聚氰胺氰脲酸(MCA)阻燃尼龙66(PA66)热降解及热释放行为分析基础上,采用包括Kissinger和Horowitz-Metzger 2种数学模型对其热降解动力学进行研究,通过热重分析(TG)、微型燃烧量热(MCC)揭示MCA与PA66的相互作用机理。结果表明,尽管不同数学模型获得的热降解活化能数值有较大差异,但MCA阻燃PA66与纯PA66相比均表现出前者活化能明显下降,由于MCA分解的三嗪化合物可与尼龙分子链氢键网络发生作用改变其电子云密度,促进其α和β-断链而形成低聚物及低分子挥发物,因此MCA会导致PA66分解温度前移,使其呈现两阶热分解特征。
Based on analysis of the behaviors of thermal degradation and thermal release, two mathematic models including Kissinger and Horowitz-Metzger were adopted to investigate the degradation dynamic mechanism of melamine cyanurate(MCA) flame retardant nylon 66(PA66) and revealed the interaction processes between MCA and PA66 through the differential thermogravimetry(TG) and micro combustion calorimetry(MCC). The results indicate that despite of different degradation active energy values resulted from the above models, the obtained values of the flame-retardant systems show an obvious decrease compared with that of PA66. Due to the hydrogen bonds interaction between the decomposition products(triazine compounds) and PA66 chains, the electron density is correspondingly changed, thus leading to α and β-scission to generate oligomers with high flowability and volatiles with low molecular weight. Accordingly, MCA causes forward shift of the degradation temperature, and makes the MCA/PA66 system display the characteristics of two stage decomposition.
Based on analysis of the behaviors of thermal degradation and thermal release, two mathematic models including Kissinger and Horowitz-Metzger were adopted to investigate the degradation dynamic mechanism of melamine cyanurate(MCA) flame retardant nylon 66(PA66) and revealed the interaction processes between MCA and PA66 through the differential thermogravimetry(TG) and micro combustion calorimetry(MCC). The results indicate that despite of different degradation active energy values resulted from the above models, the obtained values of the flame-retardant systems show an obvious decrease compared with that of PA66. Due to the hydrogen bonds interaction between the decomposition products(triazine compounds) and PA66 chains, the electron density is correspondingly changed, thus leading to α and β-scission to generate oligomers with high flowability and volatiles with low molecular weight. Accordingly, MCA causes forward shift of the degradation temperature, and makes the MCA/PA66 system display the characteristics of two stage decomposition.
引文
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[10] Kissinger H E.Reaction kinetics in differential thermal analysis [J].Anal.Chem.,1957,29:1702-1706.
[11] 刘渊,王琪.改性三聚氰胺氰尿酸盐阻燃玻纤增强PA6的研究[J].高分子材料科学与工程,2006,22(2):169-172.Liu Y,Wang Q.The studies on modified MCA flame retarded glass fiber reinforced PA6[J].Polymer Materials Science & Engineering,2006,22(2):169-172.
[12] Horowitz H H,Metzger G.A new analysis of thermogravimetric traces [J].Astron.Astrophys.,1999,353:177-185.
[13] Wang Q,Shi W.Kinetics study of thermal decomposition of epoxy resins containing flame retardant components [J].Polym.Degrad.Stab.,2006,91:1747-1754.
[2] 许冬梅,欧育湘.新一代阻燃剂次膦酸盐阻燃的玻纤增强尼龙66[J].塑料,2005,34(2):70-73.Xu D M,Ou Y X.Glass-fiber reinforced nylon 66 flame-retarded by phosphinate based flame retardant [J].Plastics,2005,34(2):70-73.
[3] Gijsman P,Steenbakkers R,Fürst C,et al.Differences in the flame retardant mechanism of melamine cyanurate in polyamide 6 and polyamide 66 [J].Polym.Degrad.Stab.,2002,78:219-224.
[4] 韩红丽,李巧玲,崔丽丽.尼龙-66的无卤阻燃研究与进展[J].合成技术及应用,2007,22(3):34-37.Han H L,Li Q L,Cui L L.Application of non-halogen flame-retardants in fire retarded PA66 [J].Synthetic Technology & Application,2007,22(3):34-37.
[5] 王丰,梁惠强,金雪峰,等.MCA阻燃PA66的研究[J].工程塑料应用,2015(2):104-107.Wang F,Liang H Q,Jin X F,et al.Study on MCA Flame Retardant PA66 [J].Engineering Plastics Application,2015(2):104-107.
[6] 李杰,刘渊,王琪.三聚氰胺氰尿酸盐/聚氨酯复合阻燃剂阻燃PA66的研究[J].塑料工业,2006,34(12):16-18.Li J,Liu Y,Wang Q.Study on flame retardation of PA66 by melamine cyanurate/TPU [J].China Plastics Industry 2006,34 (12):16-18.
[7] Li Y,Liu K,Xiao R.Preparation and characterization of flame-retarded polyamide 66 with melamine cyanurate by in situ polymerization [J].Macromol.Res.,2017,25:779-785.
[8] Casu A,Camino G,Giorgi M D,et al.Fire-retardant mechanistic aspects of melamine cyanurate in polyamide copolymer [J].Polym.Degrad.Stab.,1997,58:297-302.
[9] 徐朝芬,孙学信,郭欣.热重分析试验中影响热重曲线的主要因素分析[J].热力发电,2005,34(6):34-36.Xu C F,Sun X X,Guo X.Analysis of main factors affecting thermogravimetric curves in thermogravimetric test [J].Thermal Power Generation,2005,34(6):34-36.
[10] Kissinger H E.Reaction kinetics in differential thermal analysis [J].Anal.Chem.,1957,29:1702-1706.
[11] 刘渊,王琪.改性三聚氰胺氰尿酸盐阻燃玻纤增强PA6的研究[J].高分子材料科学与工程,2006,22(2):169-172.Liu Y,Wang Q.The studies on modified MCA flame retarded glass fiber reinforced PA6[J].Polymer Materials Science & Engineering,2006,22(2):169-172.
[12] Horowitz H H,Metzger G.A new analysis of thermogravimetric traces [J].Astron.Astrophys.,1999,353:177-185.
[13] Wang Q,Shi W.Kinetics study of thermal decomposition of epoxy resins containing flame retardant components [J].Polym.Degrad.Stab.,2006,91:1747-1754.
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